Preparation of Polypyrrole-Carbon Black Supported Pd Catalyst for Formic Acid Electrooxidation

通过低温氧化法在活性碳表面修饰聚吡咯（PPy-C）,并以PPy-C为载体制备了纳米Pd催化剂（Pd/PPy-C）.采用X射线衍射、扫描电镜、透射电镜等手段对载体PPy-C及催化剂Pd/PPy-C进行了表征,电化学测试结果表明,Pd/PPy-C催化剂电极不但能够增强催化剂对甲酸催化氧化的活性,而且还能够大幅度提高催化剂的稳定性,因此以PPy-C为载体的Pd/PPy-C催化剂是一类具有潜在应用前景的直接甲酸燃料电池阳极催化剂.通过分析电化学比表面随循环伏安次数的变化及多电势阶跃实验结果表明,催化剂电极活性衰减的主要原因是载体被氧化及电极表面积累强吸附物种的结果.     

Pd/WO_3-RGO纳米催化剂对甲酸氧化的电催化性能

采用表面修饰技术将WO_3晶粒引入到氧化石墨烯(GO)表面,通过硼氢化钾还原法制备了载钯催化剂Pd/WO_3-RGO.对催化剂进行了结构和形貌表征,并考察了该催化剂对甲酸氧化的电催化性能.结果表明,Pd/WO_3-RGO催化剂由石墨烯、单斜态WO_3和立方面心Pd晶粒组成,Pd颗粒均匀分散在载体上;使用Pd/20%WO_3-RGO催化剂电极时的甲酸氧化最大峰电流密度大幅增加,是Pd/RGO催化剂电极甲酸氧化峰电流密度的2.5倍;Pd/WO_3-RGO催化剂稳定性大大增强,且具有更加优异的抗CO中毒能力;Pd晶粒与WO_3晶粒的相互交叠有利于它们之间的催化协同效应,增强催化剂的催化性能.     

核壳结构C@WC载体的制备及Pd/C@WC催化剂对甲酸的电催化氧化

以活性碳为碳源,在碳表面原位生成碳化钨包覆的核壳结构的碳基材料(C@WC)。 TEM结果表明,制备的C@WC是具有核壳结构的碳材料,且WC中也有少量单质W。 BET比表面测量结果表明,C@WC较活性碳比表面小,但具有更多的介孔结构。 以C@WC为载体制备的Pd/C@WC催化剂电极的电化学比表积较大,为65.47 m2/g。 Pd/C@WC对甲酸的电催化氧化活性较高,氧化峰电流密度为0.222 A/cm2,比Pd/C电极上的氧化峰电流密度增加了0.128 A/cm2。 多周期循环伏安曲线的结果也表明,Pd/C@WC催化剂电极比Pd/C具有更高的活性和稳定性。     

EDTA对活性炭的功能化处理及其对炭载Pd催化剂电催化性能的影响

采用乙二胺四乙酸(EDTA)对活性炭进行功能化处理, 研究了其对表面基团、炭载Pd 纳米粒子结构及Pd催化剂电催化性能的影响. 傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)表征表明, EDTA处理在炭表面引入了含氮基团. X射线粉末衍射(XRD)光谱、透射电镜(TEM)和电化学测试结果显示, 活性炭经EDTA处理后, 负载的Pd粒子粒径虽有所增大, 但由于炭载体与Pd粒子相互作用的增强, Pd利用率增加, 催化剂对甲酸氧化的活性和稳定性均显著提高. 电化学阻抗谱(EIS)分析进一步揭示, 甲酸在该催化剂电极上的电氧化反应具有较低的电荷传递电阻.     

Pd/TiC-C催化剂对甲酸氧化的电催化性能

研究了TiC和C作混合载体的Pd(Pd/TiC-C)催化剂对甲酸氧化的电催化性能。发现Pd/TiC-C催化剂对直接甲酸燃料电池(DFAFC)中甲酸氧化的电催化性能要优于Pd/C催化剂。而且,Pd/TiC-C催化剂的电催化性能与C和TiC的质量比有关,当质量比为2时,Pd/TiC-C催化剂对甲酸氧化的电催化活性和稳定性最好,甲酸在C和TiC的质量比为2的Pd/TiC-C催化剂电极上的氧化峰峰电位为0.164 V,比在Pd/C催化剂电极上负移12 mV,峰电流密度为23.08 mA/cm2,比在Pd/C催化剂电极上高约42％。     

电解液中的乙二胺四甲叉膦酸对甲酸在炭载Pd催化剂上电氧化性能的影响

利用X射线能量色散(EDS)谱、X射线衍射(XRD)谱、透射电子显微镜(TEM)和电化学等技术研究了在电解液中添加乙二胺四甲叉膦酸(EDTMP)对甲酸在Pd/C催化剂上电氧化性能的影响. 结果表明, 当EDTMP添加的浓度为0.5 mmol/L时, Pd/C催化剂对甲酸氧化的电催化活性和稳定性最好. 这主要归结于吸附在Pd/C催化剂表面的EDTMP不但能通过基团效应降低CO的吸附量, 还能抑制Pd/C催化剂催化甲酸分解的速率, 从而减少了CO的毒化作用. 但当EDTMP的浓度大于0.5 mmol/L时, 吸附过多的EDTMP反而会占据Pd的活性位点, 降低催化作用.     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能（英文）

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料,利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上,获得Pd/C催化剂用于甲酸氧化,并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明,以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优;Pd粒径为5.4 nm,电化学活性面积为53.78 m~2/g。由于在该催化剂上甲酸氧化通过直接途径进行,Pd-AC800可用作直接甲酸燃料电池的催化剂。     

硅钨酸修饰碳载Pd催化剂对甲酸氧化的电催化性能

用络合还原法合成了用作直接甲酸燃料电池(DFAFC)中阳极碳载Pd(Pd/C)催化剂, 并研究了电解液中的硅钨酸(SiWA)对甲酸在Pd/C催化剂电极上氧化的促进作用. 结果表明, SiWA不但能提高Pd/C催化剂对甲酸氧化的电催化活性, 而且能增加电催化稳定性. 这种促进作用与SiWA浓度有关. 当SiWA浓度为0.40 g·L-1时, 促进作用最佳. 当SiWA浓度大于0.40 g·L-1时, 由于过多的SiWA吸附在Pd/C催化剂上而覆盖了部分Pd活性位点, 反而会降低促进作用. 另外, 由于SiWA在Pd/C催化剂上的吸附, 降低了CO的吸附量, 提高了Pd/C催化剂对甲酸氧化的电催化稳定性, 也促进了甲酸通过直接途径氧化.     

大孔炭载Pd催化剂对甲酸氧化的电催化性能

用X射线能量色散谱(EDS)、X射线衍射(XRD)谱、拉曼光谱和电化学技术研究和比较了直接甲酸燃料电池(DFAFC)中Vulcan XC-72炭黑载Pd (Pd/XC)和大孔炭载Pd (Pd/MC)催化剂对甲酸氧化的电催化性能. 循环伏安曲线测量表明甲酸在Pd/XC和Pd/MC催化剂电极上主要氧化峰的峰电位基本相同, 在0.15 V左右, 但在Pd/MC催化剂电极上的峰电流密度比在Pd/XC催化剂上的大30%左右. 计时电流曲线测量表明, 在6000 s时, 在Pd/MC催化剂电极上的峰电流密度比在Pd/XC催化剂上的大38%左右, 这些结果说明Pd/MC催化剂对甲酸氧化的电催化活性和稳定性要好于Pd/XC催化剂. 由于Pd/MC和Pd/XC催化剂的Pd粒子平均粒径和相对结晶度相似, 因此, Pd/MC催化剂电催化性能好的原因只能归结于MC大的孔径和高的石墨化程度引起的高电导率.     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料，利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上，获得Pd/C催化剂用于甲酸氧化，并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明，以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优；Pd粒径为5.4 nm，电化学活性面积为53.78 m²/g。由于在该催化剂上甲酸氧化通过直接途径进行，Pd-AC800可用作直接甲酸燃料电池的催化剂。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.